CN114873706B - Amorphous ferric oxide hydroxide/polyacrylamide composite flocculant and preparation method and application thereof - Google Patents
Amorphous ferric oxide hydroxide/polyacrylamide composite flocculant and preparation method and application thereof Download PDFInfo
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- CN114873706B CN114873706B CN202210621728.0A CN202210621728A CN114873706B CN 114873706 B CN114873706 B CN 114873706B CN 202210621728 A CN202210621728 A CN 202210621728A CN 114873706 B CN114873706 B CN 114873706B
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- amorphous
- ferric
- composite flocculant
- polyacrylamide composite
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 25
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 14
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 36
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 229910001439 antimony ion Inorganic materials 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 24
- 229910052787 antimony Inorganic materials 0.000 abstract description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011550 stock solution Substances 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000008394 flocculating agent Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 13
- -1 hydroxyl ferric oxide Chemical compound 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 229910002588 FeOOH Inorganic materials 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000005189 flocculation Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000016615 flocculation Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000012982 microporous membrane Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The application relates to an amorphous iron oxyhydroxide/polyacrylamide composite flocculant, a preparation method and application thereof, wherein the preparation method of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant comprises the following steps: s1, mixing ferric salt, a first solvent and bicarbonate, stirring for 10-24 hours at room temperature, and carrying out suction filtration, washing, drying and grinding to obtain amorphous ferric hydroxide; s2, carrying out polymerization reaction on the amorphous ferric hydroxide obtained in the step S1, acrylamide and an initiator under the protection of inert gas, and precipitating a polymer after the reaction is finished to obtain the amorphous ferric hydroxide/polyacrylamide composite flocculant. The composite flocculant is used for removing heavy metal ion antimony in wastewater, has the advantages of simple preparation method, low raw material price, less dosage, stable effect and wide pH application range, and can efficiently remove antimony in water.
Description
Technical Field
The application relates to the technical field of wastewater treatment containing heavy metal ions, in particular to an amorphous ferric oxide hydroxide/polyacrylamide composite flocculant, and a preparation method and application thereof.
Background
For the removal of antimony, coagulating sedimentation is widely used because of its advantages of simple operation, low cost, and the like. However, for low concentrations of antimony in water, conventional flocculants are not effective in removal and are greatly affected by water quality conditions. Therefore, development of a novel flocculant which is efficient, stable, little affected by water quality conditions and capable of effectively removing trace antimony in water is urgently needed.
Iron oxyhydroxide is a mineral material with rich and nontoxic reserves, stable chemical property, large specific surface area, fine particle structure and strong adsorption capacity, and is of great concern in heavy metal ion treatment. But the well-crystallized iron oxyhydroxide nanoparticles have a structure that is difficult to expand or contract, which limits ion permeation and diffusion. In addition, iron oxyhydroxide nanoparticles are prone to aggregation, reducing their adsorption activity, which limits their use in water treatment.
The prior art CN 109046226B discloses a preparation method and application of a hydroxyl ferric oxide nano-sheet for treating anionic dye sewage, wherein a sodium borohydride solution is dropwise added into a specific iron salt aqueous solution, a controllable liquid phase is reduced to generate a precursor, and the obtained precursor is subjected to post-treatment by absolute ethyl alcohol and is dried and oxidized in air to obtain the hydroxyl ferric oxide nano-sheet; the prepared iron oxyhydroxide nano sheet is of an amorphous structure, the thickness of a sheet layer is 1-4nm, the specific surface area is larger, and the iron oxyhydroxide nano sheet has stronger adsorption and photocatalytic degradation capability on azo dyes in wastewater, so that the high-efficiency decontamination of the wastewater can be realized. However, the iron oxyhydroxide prepared in fig. 4 of the specification has a distinct crystalline structure, indicating that it results in a crystalline iron oxyhydroxide rather than an amorphous structure.
The prior art CN 112691666A discloses an amorphous iron oxyhydroxide-biochar composite material and a preparation method thereof, and relates to the technical field of amorphous materials. The preparation method provided by the method comprises the following steps: carbonizing biomass containing silicon dioxide to obtain a biochar material; mixing the biochar material with an iron salt aqueous solution, and performing hydrothermal reaction under an alkaline condition to obtain the amorphous iron oxyhydroxide-biochar composite material. On the one hand, the biochar material can be used as a carrier of a composite material, and meanwhile, silicon dioxide in the biochar material also provides a necessary silicon source for inhibiting the crystallization of the ferric oxyhydroxide, so that the structural disorder of the ferric oxyhydroxide is ensured, and the amorphous ferric oxyhydroxide-biochar composite material is obtained. However, the preparation temperature is higher, the reaction is required under the conditions of high pressure and high alkali, the reaction condition is not easy to control, and the prepared biochar adsorption material is not a flocculant.
Disclosure of Invention
The application aims at providing a preparation method of an amorphous ferric hydroxide/polyacrylamide composite flocculant; the second purpose of the application is to provide an application of the amorphous ferric hydroxide/polyacrylamide composite flocculant in the efficient removal of antimony ions in wastewater.
In order to solve the technical problems, the technical scheme of the application is as follows:
the preparation method of the amorphous ferric oxide hydroxide/polyacrylamide composite flocculant comprises the following steps:
s1, mixing ferric salt, a first solvent and bicarbonate, stirring for 10-24 hours at room temperature, and carrying out suction filtration, washing, drying and grinding to obtain amorphous ferric hydroxide;
s2, carrying out polymerization reaction on the amorphous ferric hydroxide obtained in the step S1, acrylamide and an initiator under the protection of inert gas, and precipitating a polymer after the reaction is finished to obtain the amorphous ferric hydroxide/polyacrylamide composite flocculant.
Preferably, in S1, the molar ratio of ferric ion to bicarbonate is (1-2): 3-7.
Too small a bicarbonate amount is difficult to fully react iron ions, while too large a bicarbonate content results in bicarbonate waste.
Preferably, in S1, the mass ratio of ferric ion to the first solvent is 0.168-0.336:30.
The solvent is too small in dosage, iron ions and bicarbonate are difficult to be effectively mixed to react, the generation proportion of amorphous ferric hydroxide is influenced, the effect of inhibiting crystalline ferric oxide cannot be achieved, and the solvent is wasted due to the too large dosage.
Preferably, the bicarbonate is one or more of ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate or lithium bicarbonate.
Preferably, the first solvent is an alcoholic solvent, preferably methanol or ethanol.
Further preferably, the first solvent is ethanol (economical and non-toxic).
The first solvent plays a role in inhibiting crystallization of the iron oxyhydroxide during the preparation process of the amorphous iron oxyhydroxide.
Preferably, in S1, the ferric salt is ferric sulfate, ferric chloride and/or ferric nitrate with or without water of crystallization.
Preferably, in S2, the mass ratio of the amorphous ferric hydroxide to the acrylamide is 1.06-6.36:6.
The amorphous ferric hydroxide has the mass ratio of less than 10 percent, the flocculation effect is poor, and the amorphous ferric hydroxide mainly absorbs and guides antimony ions in water.
The amorphous ferric oxide hydroxide has the mass ratio higher than 40%, the flocculation effect is poor, the amorphous ferric oxide hydroxide has the excessively high ratio, aggregation is easy to occur, the adsorption active sites of the amorphous ferric oxide hydroxide cannot be fully exerted, at the moment, the proportion of the polyacrylamide component is low, flocs are difficult to form in the flocculation process, and antimony ions cannot be removed by sedimentation.
Further preferably, in S2, the mass ratio of amorphous iron oxyhydroxide to acrylamide is 4.10:6.
The amorphous ferric oxide has the best effect with the proportion of 30%, at the moment, the adsorption active site of the amorphous ferric oxide is fully exposed, and the polyacrylamide can also exert the best flocculation capacity at the same time, so that the best antimony removal effect is achieved.
Preferably, in S2, after dispersing the amorphous iron oxyhydroxide obtained in S1 in the second solvent, acrylamide is added under the protection of nitrogen to perform polymerization reaction.
Preferably, the dispersion is an ultrasonic dispersion.
Preferably, the second solvent is deionized water or ethanol.
Since the polymerization process needs to be carried out in a dissolved state, and polyacrylamide can be mutually dissolved with water in any proportion, the polymerization solvent is deionized water.
Preferably, in S2, the initiator is a mixture of an oxidizing agent and a reducing agent.
The reducing agent reacts with the oxidizing agent to generate free radicals, thereby initiating polymerization of the acrylamide monomer.
Further preferably, the oxidant is one or more of ammonium persulfate, sodium persulfate and potassium persulfate, preferably ammonium persulfate.
Further preferably, the reducing agent is one or more of sodium bisulphite, sodium thiosulfate, ascorbic acid and glucose, preferably sodium bisulphite.
Preferably, in S2, the mass ratio of ammonium persulfate to sodium bisulfite is 1-2:1.
The sodium bisulphite is too small in dosage, so that the ammonium persulfate is difficult to excite to generate free radicals, and the polymerization reaction cannot be initiated; and when the dosage of sodium bisulphite is too large, the sodium bisulphite can react with generated free radicals to block the polymerization reaction.
Preferably, to S2, 1-2ml of ammonium persulfate with a mass concentration of 1% and 1ml of sodium bisulphite with a mass concentration of 1% are added.
The addition amount of the initiator is too small, so that the polymerization reaction is difficult to initiate; the addition of the initiator is too large, the polymerization degree of the polymer is too high, and the flocculation effect is affected.
Preferably, in S2, the polymer is precipitated using an organic solvent.
Preferably, the organic solvent is methanol, ethanol, acetone, diethyl ether, aliphatic hydrocarbon, or aromatic hydrocarbon.
Polyacrylamide is insoluble in most organic solvents such as methanol, ethanol, acetone, diethyl ether, aliphatic and aromatic hydrocarbons.
Preferably, in S2, the method further comprises the steps of drying and grinding the obtained amorphous ferric hydroxide/polyacrylamide composite flocculant.
Preferably, the drying temperature is 40-70 ℃.
The drying temperature should not be too high, otherwise the amorphous iron oxyhydroxide in the amorphous iron oxyhydroxide/polyacrylamide composite flocculant will be oxidized to crystalline iron oxyhydroxide or iron oxide. The temperature is too low to be effectively dried.
The grinding is to accelerate the dissolution of the flocculant in the wastewater. Thus, the particle size is generally controlled to be small.
Based on the same inventive concept, the application also provides application of the amorphous ferric oxide hydroxide/polyacrylamide composite flocculant in wastewater treatment.
Based on the same inventive concept, the application also provides application of the amorphous ferric hydroxide/polyacrylamide composite flocculant in removing antimony ions in wastewater.
Preferably, the amorphous ferric hydroxide/polyacrylamide composite flocculant is added into wastewater containing antimony ions with a certain turbidity, and the wastewater is subjected to stage coagulation treatment.
Preferably, the pH value of the wastewater is 4-9.
Preferably, the wastewater contains Cl - 、NO 3 - 、HCO 3 - 、PO 4 3- 、SO 4 2- Or humic acid.
The application is further explained below:
bicarbonate reacts with iron ions as follows:
Fe 3+ +3HCO 3 - →FeOOH+H 2 O+3CO 2
in this process, the hydroxyl groups in the alcohol solvent can be combined with the iron ions, thereby inhibiting the crystallization process of the iron ions. Therefore, the process should strictly control the molar ratio of bicarbonate to iron ions, so that the bicarbonate is slightly excessive to iron ions, and the aim of completely reacting the iron ions is fulfilled.
The reaction process of the amorphous ferric hydroxide/polyacrylamide composite flocculant comprises the following steps: the method comprises the following physical and chemical processes:
the branched amino groups of the polyacrylamide can complex with iron in the amorphous iron oxyhydroxide, thereby fixing the amorphous iron oxyhydroxide to the polyacrylamide. Another part of amorphous iron oxyhydroxide can be attached in the holes on the surface of polyacrylamide by physical adsorption.
Compared with the prior art, the application has the following beneficial effects:
(1) The preparation method of the application does not involve high temperature and high pressure, and has low energy consumption, simple flow and low raw material cost.
(2) The flocculant prepared by the application has a treatment effect on wastewater in the pH range of 4-9, which is obviously better than that of crystalline ferric hydroxide/polyacrylamide and traditional commercial flocculant polymeric ferric sulfate;
(3) The amorphous ferric oxide/polyacrylamide composite flocculant can treat antimony-containing wastewater in a wider concentration range, can treat high-concentration antimony-containing wastewater with a smaller dosage, is basically not influenced by common ions in other wastewater, has stable effect, basically does not influence the treatment effect under wide-range pH fluctuation (4-10), and has wide application range.
(4) The flocculant prepared by the application can be used for emergency treatment of antimony leakage accidents.
Drawings
FIG. 1 is a synthetic route diagram of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1;
FIG. 2 is a scanning electron microscope image of the amorphous iron oxyhydroxide prepared in example 1;
FIG. 3 is a scanning electron microscope image of acrylamide;
FIG. 4 is a scanning electron microscope image of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1;
FIG. 5 is a BET analysis of the amorphous iron oxyhydroxide, polyacrylamide, and amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1;
FIG. 6 is an amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in examples 1-4;
FIG. 7 is an X-ray diffraction pattern of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1;
FIG. 8 is a graph showing the effect of removing antimony ions of the amorphous iron oxyhydroxide/polyacrylamide composite flocculants prepared in examples 1 to 4;
FIG. 9 shows the effect of removing antimony ions in the range of 20-200mg/L of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1;
FIG. 10 shows the effect of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant obtained in example 1 on removal of antimony ions from water by coagulation at different pH values;
FIG. 11 is a graph showing the antimony ion removal effect of the amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1 in comparison with a commercial polymeric ferric sulfate flocculant (PFS) and a crystalline iron oxyhydroxide/polyacrylamide composite flocculant;
FIG. 12 is a graph of the study of anions (Cl) that are widely present in an aqueous environment - 、NO 3 - 、HCO 3 - 、SO 4 2- ) The effect of removing antimony ions in water by using the amorphous iron oxyhydroxide/polyacrylamide composite flocculant obtained in example 1 is provided.
Detailed Description
The application will be described in detail below with reference to the drawings in connection with embodiments. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Example 1
In this example, the amorphous iron oxyhydroxide/polyacrylamide composite flocculant was prepared as follows:
(1) Weighing 3mmol of ferric chloride hexahydrate, dissolving in 40ml of ethanol, adding 9mmol of ammonium bicarbonate, stirring at room temperature for 12 hours, filtering, washing with ethanol for several times, vacuum drying at 60 ℃, and grinding to obtain the product; the scanning electron microscope image of the obtained amorphous iron oxyhydroxide powder is shown in fig. 2. The amorphous iron oxyhydroxide powder has smaller particle size and more uniform particle size distribution.
(2) 4.10g of the prepared amorphous iron oxyhydroxide is weighed, dissolved in 30ml of ultrapure water, dispersed by ultrasonic for 10min, added with 6g of acrylamide, continuously stirred and introduced with nitrogen, after 20min, added with 1.6ml of each of ammonium persulfate and sodium bisulfate solution with the mass fraction of 1%, and continuously stirred for 6h under the protection of nitrogen. After the polymerization reaction is finished, the polymer is precipitated by acetone, dried at 60 ℃, crushed and ground to obtain the amorphous iron oxyhydroxide/polyacrylamide composite material with the iron content fraction of 30 percent, and the amorphous iron oxyhydroxide/polyacrylamide composite material is marked as 30 percent FeOOH/PAM.
Scanning electron microscopy analysis was performed on amorphous iron oxyhydroxide as shown in fig. 2. The results show that: the amorphous iron oxyhydroxide particles are uniformly distributed and have no fixed morphology.
The polyacrylamide was subjected to scanning electron microscopy analysis as shown in fig. 3. The results show that: the surface of the polyacrylamide is smoother, and holes are distributed more.
Scanning electron microscopy was performed on 30% FeOOH/PAM and the results are shown in FIG. 4. The results show that: the surface of the amorphous ferric oxide hydroxide/polyacrylamide composite material is rough, and the holes on the surface of the original polyacrylamide are filled with more amorphous ferric oxide hydroxide.
The specific surface area analysis was performed on the amorphous iron oxyhydroxide powder, acrylamide, and 30% FeOOH/PAM, respectively, and the results are shown in FIG. 5. The results show that: the specific surface area of the amorphous iron oxyhydroxide powder was 40.525m 3 The specific surface area of the amorphous iron oxyhydroxide/polyacrylamide composite material is greatly improved, and the specific surface area is up to 110.002m 3 /g。
Example 2
Example 1 was repeated, except that the amorphous iron oxyhydroxide in this example was added in an amount of 2.40g, unlike example 1.
The amorphous iron oxyhydroxide/polyacrylamide composite material obtained is marked as 20% FeOOH/PAM.
Example 3
Example 1 was repeated, except that the amorphous iron oxyhydroxide in this example was added in an amount of 3.18g, unlike example 1.
The amorphous iron oxyhydroxide/polyacrylamide composite material obtained was marked as 25% FeOOH/PAM.
Example 4
Example 1 was repeated, except that the addition amount of amorphous iron oxyhydroxide in this example was 6.36g.
The amorphous iron oxyhydroxide/polyacrylamide composite material obtained was marked as 40% FeOOH/PAM.
The amorphous iron oxyhydroxide/polyacrylamide composites obtained in examples 1-4 were photographed, and the resulting powder patterns are shown in fig. 6. The more amorphous iron oxyhydroxide is added, the more red the color of the composite.
The amorphous iron oxyhydroxide/polyacrylamide composites obtained in examples 1-4 were tested for X-ray diffraction and the results obtained are shown in fig. 7: all of the amorphous iron oxyhydroxide/polyacrylamide composites prepared in examples had no significant diffraction peaks, indicating that the iron oxyhydroxide/polyacrylamide composites prepared in examples 1-4 were amorphous composites.
Example 5
The method for removing antimony ions in water by coagulation by using the amorphous ferric hydroxide/polyacrylamide composite flocculant obtained in the examples 1-4 is provided, and comprises the following specific steps:
(1) Preparing a simulated water sample: preparing a stock solution of antimony ions with the concentration of 20mg/L, and storing at the temperature of 4 ℃ for later use; weighing 2g of kaolin, and dissolving in 1L of deionized water to prepare turbidity stock solution; 10ml of turbidity stock solution is added into 1L of tap water, and after stirring until the turbidity is stable, 1ml of antimony ion stock solution is added, and further stirring is carried out uniformly to prepare a simulated water sample.
(2) And placing the beaker filled with the pre-prepared antimonic test water sample into a six-link stirrer for coagulation beaker test. Firstly, rapidly stirring for 1min at 200r/min until turbidity of a water sample is stable, adjusting pH to 6, then adding a flocculating agent (200 mg/L) according to a dose set by a test, rapidly stirring for 2min at 200r/min, slowly stirring for 10min at 60r/min, and standing for precipitation for 10min.
Collecting the supernatant, filtering with 0.22 μm microporous membrane, and measuring the concentration of residual antimony ion with fluorescence spectrophotometer.
As shown in FIG. 8, the amorphous ferric hydroxide/polyacrylamide composite flocculant prepared in examples 1-4 has excellent effect of removing antimony ions, and the concentration of antimony in effluent is below 5 mug/L, thereby meeting the requirements of national sanitary Standard for Drinking Water GB 5749-2022.
Example 6
The method for removing antimony ions in water by using the amorphous ferric hydroxide/polyacrylamide composite flocculant obtained in the example 1 is provided, and the method comprises the following specific steps:
(1) Preparing a simulated water sample: preparing stock solution of antimony ions, wherein the concentration of the stock solution is 20mg/L, 40mg/L, 60mg/L and 120mg/L, and storing the stock solution at 4 ℃ for later use; weighing 2g of kaolin, and dissolving in 1L of deionized water to prepare turbidity stock solution; 10ml of turbidity stock solution is added into 1L of tap water, and after stirring until the turbidity is stable, 1ml of antimony ion stock solution is added, and further stirring is carried out uniformly to prepare a simulated water sample. The concentration of antimony ions in the obtained simulated water sample is 20 mug/L, 40 mug/L, 60 mug/L and 120 mug/L respectively.
(2) The beaker filled with the pre-prepared antimonic test water sample is placed in a six-link stirrer for coagulation beaker test, firstly, the mixture is rapidly stirred for 1min at 200r/min until turbidity of the water sample is stable, the pH value is adjusted to be 6, then, a flocculating agent (20-140 mg/L of the amorphous ferric hydroxide/polyacrylamide composite flocculating agent obtained in example 1 respectively) is added according to the dose set by the test, then, the mixture is rapidly stirred for 2min at 200r/min, slowly stirred for 10min at 60r/min, and the mixture is stood for precipitation for 10min.
Collecting the supernatant, filtering with 0.22 μm microporous membrane, and measuring the concentration of residual antimony ion with fluorescence spectrophotometer.
As shown in FIG. 9, the removal rate of Sb (V) increased with the addition of the flocculant, the concentration of Sb (V) was in the range of 20-60. Mu.g/L, and when the addition of the flocculant was 20mg/L or more, the removal rate of Sb (V) was 90.5% or more, and the concentration of Sb in the effluent satisfied the requirements. Continuously increasing the adding amount of the flocculant to 140mg/L, and keeping the removal rate of Sb (V) stable. For the case of high concentration of Sb (V) of 120 mug/L, the addition amount of 60mg/L of a smaller flocculating agent can remove 85.6% of Sb (V). Therefore, the amorphous ferric oxide hydroxide/polyacrylamide composite flocculant can treat antimony-containing wastewater in a wider concentration range, and can treat high-concentration antimony-containing wastewater with a smaller dosage. From the viewpoints of economy and effect, the dosage of the flocculant which is 20mg/L is suitable for experiments.
Example 7
The method for removing antimony ions in water by using the amorphous ferric hydroxide/polyacrylamide composite flocculant obtained in the example 1 is provided, and the method comprises the following specific steps:
(1) Preparing a simulated water sample: preparing a stock solution of antimony ions, wherein the concentration of the stock solution is 20mg/L, and storing the stock solution at the temperature of 4 ℃ for later use; weighing 2g of kaolin, and dissolving in 1L of deionized water to prepare turbidity stock solution; 10ml of turbidity stock solution is added into 1L of tap water, and after stirring until the turbidity is stable, 1ml of antimony ion stock solution is added, and further stirring is carried out uniformly to prepare a simulated water sample. The concentration of antimony ions in the obtained simulated water sample is 20 mug/L.
(2) And placing the beaker filled with the pre-prepared antimonic test water sample into a six-link stirrer for coagulation beaker test. Firstly, rapidly stirring for 1min at 200r/min until turbidity of a water sample is stable, adjusting pH values to be 2-10 respectively, then adding flocculating agents (200 mg/L of the amorphous ferric hydroxide/polyacrylamide composite flocculating agents obtained in example 1 respectively) according to the set doses of experiments, rapidly stirring for 2min at 200r/min, slowly stirring for 10min at 60r/min, and standing for precipitation for 10min.
Collecting the supernatant, filtering with 0.22 μm microporous membrane, and measuring the concentration of residual antimony ion with fluorescence spectrophotometer.
As can be seen from fig. 10, the removal rate showed a rapid increase trend as the pH of the solution increased from 2 to 4. The removal rate of FeOOH/PAM to Sb (V) is kept above 92.8% in the pH range of 4-10. Considering that the pH range of natural water is 6.5-8.5, the amorphous ferric hydroxide/polyacrylamide composite flocculant can be completely suitable for practical water without pH adjustment, and can adapt to pH fluctuation in a wider range.
Example 8
The method for removing antimony ions in water by using various flocculating agents at different pH values comprises the following specific steps:
(1) Preparing a simulated water sample: preparing a stock solution of antimony ions with the concentration of 100mg/L, and storing at the temperature of 4 ℃ for later use; weighing 2g of kaolin, and dissolving in 1L of deionized water to prepare turbidity stock solution; 10ml of turbidity stock solution is added into 1L of tap water, and after stirring until the turbidity is stable, 1ml of antimony ion stock solution is added, and further stirring is carried out uniformly to prepare a simulated water sample. The concentration of antimony ions in the obtained simulated water sample is 100 mug/L.
(2) And placing the beaker filled with the pre-prepared antimonic test water sample into a six-link stirrer for coagulation beaker test. Firstly, rapidly stirring for 1min at 200r/min until turbidity of a water sample is stable, adjusting pH values to be 4, 6, 7 and 9 respectively, then adding flocculating agents (20 mg/L of the amorphous ferric hydroxide/polyacrylamide composite flocculating agent, 20mg/L of the crystalline ferric hydroxide/polyacrylamide composite flocculating agent and 20mg/L of commercial polymeric ferric sulfate obtained in example 1 respectively) according to the set doses of experiments, rapidly stirring for 2min at 200r/min, slowly stirring for 10min at 60r/min, and standing for precipitation for 10min.
The preparation method of the crystalline ferric oxide/polyacrylamide composite flocculant comprises the following steps: dissolving 0.5g of ferric sulfate and 0.6g of urea in 40mL of distilled water, uniformly mixing, pouring into a 100mL polytetrafluoroethylene high-pressure reaction kettle, transferring to a 100 ℃ oven for hydrothermal reaction for 5 hours, centrifuging to collect a sample, and drying at 60 ℃ to obtain crystalline ferric hydroxide.
4.10g of the prepared crystalline ferric hydroxide is weighed, dissolved in 30ml of ultrapure water, dispersed for 10min by ultrasonic, 6g of acrylamide is added, continuous stirring is carried out, nitrogen is introduced, after 20min, 1.6ml of ammonium persulfate and sodium bisulfate solution with mass fraction of 1% are added, and continuous stirring is carried out for 6h under the protection of nitrogen. And after the polymerization reaction is finished, precipitating the polymer by using acetone, drying at 60 ℃, crushing and grinding to obtain the crystalline ferric hydroxide/polyacrylamide composite material with the iron content fraction of 30%.
Collecting the supernatant, filtering with 0.22 μm microporous membrane, and measuring the concentration of residual antimony ion with fluorescence spectrophotometer.
As can be seen from FIG. 11, the amorphous iron oxyhydroxide/polyacrylamide composite flocculant prepared in example 1 has better antimony ion removal effect than commercial Polymeric Ferric Sulfate (PFS) and crystalline iron oxyhydroxide/polyacrylamide composite flocculants in the pH range of 4-9.
Example 9
Investigation of anions (Cl) widely present in aqueous environments - 、NO 3 - 、HCO 3 - 、SO 4 2- ) The effect of removing antimony ions in water by using the amorphous iron oxyhydroxide/polyacrylamide composite flocculant obtained in example 1 is provided. The method comprises the following specific steps:
(1) Preparing a simulated water sample: preparing a stock solution of antimony ions with the concentration of 20mg/L, and storing at the temperature of 4 ℃ for later use; weighing 2g of kaolin, and dissolving in 1L of deionized water to prepare turbidity stock solution; adding 10ml of turbidity stock solution into 1L of tap water, stirring until the turbidity is stable, and adding 1ml of antimony ion stock solution, wherein the concentration of antimony ions in the obtained simulated water sample is 20 mug/L; 0mg/L, 20mg/L, 40mg/L, 60mg/L, 80mg/L of Cl is adopted - 、NO 3 - 、HCO 3 - 、SO 4 2- And simulating coexisting ions in the water body, adding sodium chloride (analytically pure), sodium nitrate (analytically pure), sodium bicarbonate (analytically pure) or sodium sulfate (analytically pure) and the like into the test water sample according to research requirements, and adjusting the pH value of the water sample by utilizing hydrochloric acid and sodium hydroxide (analytically pure). Further stirring uniformly to prepare the simulated water sample.
(2) The beaker filled with the pre-prepared antimonic test water sample is placed in a six-link stirrer for coagulation beaker test, firstly, the stirring is fast carried out for 1min at 200r/min until turbidity of the water sample is stable, the pH values are respectively adjusted to 7, then, a flocculating agent (80 mg/L of the amorphous ferric hydroxide/polyacrylamide composite flocculating agent obtained in example 1) is added according to the dose set by the test, and then the stirring is fast carried out for 2min at 200r/min, the stirring is slow carried out for 10min at 60r/min, and the standing and the precipitation are carried out for 10min.
Collecting the supernatant, filtering with 0.22 μm microporous membrane, and measuring the concentration of residual antimony ion with fluorescence spectrophotometer.
As can be seen from fig. 12, the flocculation removal of Sb (V) ions by the coexisting anions showed a slight inhibition effect, the extent of which was in turn: cl - <NO 3 - <HCO 3 - <SO 4 2- . Wherein the monovalent anion (Cl) - 、NO 3 - 、HCO 3 - ) The effect on the removal rate of Sb (V) is small, even if the concentration of anions reaches 80mg/L, the Sb (V) is dischargedThe water concentration can also be satisfactory. While when SO 4 2- When the concentration of the Sb (V) ion reaches 40mg/L, the flocculation removal rate of the Sb (V) ion can still reach more than 80%. Therefore, the amorphous ferric oxide hydroxide/polyacrylamide composite flocculant is not easily influenced by anions in a water body.
In conclusion, the preparation method of the amorphous ferric hydroxide/polyacrylamide composite flocculant does not involve high temperature and high pressure, has low energy consumption, simple flow and low raw material price, can efficiently remove antimony in water, can treat antimony-containing wastewater with a wider concentration range, can treat high-concentration antimony-containing wastewater with a smaller dosage, is basically not influenced by common ions in other wastewater, has stable effect, and has wide application range, wherein the pH of the wastewater can fluctuate from 4-8 in a large range without basically influencing the treatment effect.
The foregoing examples are set forth in order to provide a more thorough description of the present application and are not intended to limit the scope of the application, and various modifications of the application, which are equivalent to those skilled in the art upon reading the present application, will fall within the scope of the application as defined in the appended claims.
Claims (7)
1. The application of the amorphous ferric oxide/polyacrylamide composite flocculant in removing antimony ions in wastewater is characterized in that the preparation method of the amorphous ferric oxide/polyacrylamide composite flocculant comprises the following steps:
s1, mixing ferric salt, a first solvent and bicarbonate, stirring for 10-24 hours at room temperature, and carrying out suction filtration, washing, drying and grinding to obtain amorphous ferric hydroxide; s2, carrying out polymerization reaction on the amorphous ferric hydroxide obtained in the step S1, acrylamide and an initiator under the protection of inert gas, and precipitating a polymer after the reaction is finished to obtain the amorphous ferric hydroxide/polyacrylamide composite flocculant;
in S1, the mole ratio of ferric ion and bicarbonate is (1-2): (3-7);
in S1, the mass ratio of ferric ions to the first solvent is 0.168-0.336:30; the first solvent is an alcohol solvent; in S2, the mass ratio of the amorphous ferric oxide hydroxide to the acrylamide is 1.06-6.36:6, preparing a base material;
the addition amount of the amorphous ferric oxide hydroxide/polyacrylamide composite flocculant is 20mg/L.
2. The use according to claim 1, wherein the bicarbonate is one or more of ammonium bicarbonate, sodium bicarbonate or potassium bicarbonate; the first solvent is methanol or ethanol; ferric salts are ferric sulfate, ferric chloride and/or ferric nitrate with or without water of crystallization.
3. The use according to claim 1, wherein in S2 the mass ratio of amorphous iron oxyhydroxide to acrylamide is 4.10:6.
4. the process according to claim 1, wherein in S2, the amorphous iron oxyhydroxide obtained in S1 is dispersed in a second solvent and then polymerized by adding acrylamide under nitrogen protection.
5. The use according to claim 4, wherein the second solvent is deionized water or ethanol.
6. The use according to claim 1, wherein in S2, the initiator is in a mass ratio of (1-2): 1 a mixture of an oxidizing agent and a reducing agent; the oxidant is one or more of ammonium persulfate, sodium persulfate and potassium persulfate; the reducing agent is one or more of sodium bisulphite, sodium thiosulfate, ascorbic acid and glucose.
7. The use according to claim 1, characterized in that the pH of the waste water is 4-9.
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